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EP2365938B1 - Method for desulphurization - Google Patents

Method for desulphurization Download PDF

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Publication number
EP2365938B1
EP2365938B1 EP09778825.1A EP09778825A EP2365938B1 EP 2365938 B1 EP2365938 B1 EP 2365938B1 EP 09778825 A EP09778825 A EP 09778825A EP 2365938 B1 EP2365938 B1 EP 2365938B1
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EP
European Patent Office
Prior art keywords
gas
claus plant
residual gas
carbon dioxide
combustion
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Application number
EP09778825.1A
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German (de)
French (fr)
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EP2365938A2 (en
Inventor
Johannes Menzel
Olaf Von Morstein
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ThyssenKrupp Industrial Solutions AG
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ThyssenKrupp Industrial Solutions AG
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Priority to PL09778825T priority Critical patent/PL2365938T3/en
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/02—Preparation of sulfur; Purification
    • C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
    • C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
    • C01B17/0456—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process the hydrogen sulfide-containing gas being a Claus process tail gas
    • C—CHEMISTRY; METALLURGY
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/02—Preparation of sulfur; Purification
    • C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/52—Hydrogen sulfide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/75—Multi-step processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8603—Removing sulfur compounds
    • B01D53/8612—Hydrogen sulfide
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    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/02—Preparation of sulfur; Purification
    • C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
    • C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
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    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/02—Preparation of sulfur; Purification
    • C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
    • C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
    • C01B17/0408—Pretreatment of the hydrogen sulfide containing gases
    • C—CHEMISTRY; METALLURGY
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    • C01B17/02—Preparation of sulfur; Purification
    • C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
    • C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
    • C01B17/0413—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process characterised by the combustion step
    • C—CHEMISTRY; METALLURGY
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B01D2251/10—Oxidants
    • B01D2251/102—Oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2251/00—Reactants
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    • B01D2251/202—Hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2256/16—Hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/20—Carbon monoxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/22—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/304—Hydrogen sulfide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
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    • B01D2257/306—Organic sulfur compounds, e.g. mercaptans
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B01D2257/30—Sulfur compounds
    • B01D2257/308—Carbonoxysulfide COS
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/502—Carbon monoxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B01D2257/80—Water
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77—Liquid phase processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01D53/34—Chemical or biological purification of waste gases
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
    • C—CHEMISTRY; METALLURGY
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0485—Composition of the impurity the impurity being a sulfur compound
    • C—CHEMISTRY; METALLURGY
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0495—Composition of the impurity the impurity being water
    • C—CHEMISTRY; METALLURGY
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
    • C01B2203/86—Carbon dioxide sequestration
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry

Definitions

  • the invention relates to a process for desulfurization, wherein a gas mixture for separating acidic gas components is subjected to a separation process in which a sour gas comprising carbon dioxide and sulfur compounds, in particular hydrogen sulfide, is formed.
  • a sour gas comprising carbon dioxide and sulfur compounds, in particular hydrogen sulfide
  • acidic gas components are first removed from the gas stream with a suitable absorbent and thus separated from a Nutzgaskomponente.
  • the sour gas components contained are released and subsequently fed to a Claus plant.
  • the Claus process is carried out such that the sour gas is burned with air, wherein the hydrogen sulfide (H 2 S) with the oxygen contained in the combustion air (O 2 ) to elemental sulfur and water (H 2 O) is reacted and the elemental sulfur (S) is separated by subsequent cooling in capacitors (" Ullmann's Encyclopedia of Industrial Chemistry, Volume 10, 4th edition 1975, page 594 ).
  • H 2 S hydrogen sulfide
  • O 2 O elemental sulfur and water
  • S elemental sulfur
  • capacitors Ullmann's Encyclopedia of Industrial Chemistry, Volume 10, 4th edition 1975, page 594
  • Carbon dioxide contributes to the global greenhouse effect as so-called climate gas, there is a need to increase the additional release of carbon dioxide avoid. Furthermore, processes are also currently known which require large amounts of carbon dioxide as a process gas. Carbon dioxide, for example, can be used to increase the yield during oil production, whereby carbon dioxide is injected into an oil reservoir ("Enhanced Oil Recovery" EOR). Both for the sequestration of carbon dioxide to avoid emissions as well as for technical use, the carbon dioxide usually has to be separated with a considerable effort of other components, such as nitrogen.
  • EOR Enhanced Oil Recovery
  • the publication EP 0 059 412 A2 relates to a method for controlling the amount of ballast gas in a combustion process, in particular in the operation of a Claus plant, wherein the residual gas formed is discharged in a conventional manner to the environment.
  • it is provided to supply air and technically pure oxygen, wherein the ratio of air and technically pure oxygen is adapted to the respectively present inert gas in the fuel gas.
  • the term technically pure oxygen refers to a gas which for the most part consists of oxygen and is formed in a conventional large-scale production process. The purity is usually more than 90%, in the case of cryogenic decomposition methods typically at least 98%.
  • EP 1914 294 A1 is a generic method for removing sulfur components, such as hydrogen sulfide and mercaptans, described from natural gas.
  • sulfur components such as hydrogen sulfide and mercaptans
  • For the removal of hydrogen sulfide and carbon dioxide is first carried out a scrubbing of the natural gas, whereupon a conversion of the mercaptans into hydrogen sulfide takes place in the largest possible volume of gas.
  • Carbon dioxide and hydrogen sulfide are then fed to a Claus plant in which sulfur is then recovered. Emerging from the Claus reactor residual gas can be further treated in a SCOT ® process to reduce the sulfur content of the residual gas on.
  • WO 2008/103467 A1 describes a method by which hydrogen and carbon dioxide can be recovered from a syngas stream.
  • hydrogen sulfide is removed in a first step and carbon dioxide in a second step from the gas mixture.
  • different absorbers are used.
  • the withdrawn hydrogen sulfide is used for sulfur recovery.
  • US 5,628,977 is a method for the desulfurization of hydrogen sulfide-containing exhaust gases known. Most of the hydrogen sulfide is removed from the exhaust gases in a Claus plant. The leaving the Claus plant gas contains, for example, due to incomplete combustion hydrogen sulfide, hydrogen cyanide, ammonia, carbonyl compounds, phenols and other hydrocarbons. In order to reduce the environmental impact, it is proposed to use the calorific value of the gases present in the residual gas, in particular carbon monoxide, hydrogen, hydrogen sulfide, sulfur vapor and organic compounds, by combustion. The sulfur dioxide produced in the combustion process is recycled and fed to the Claus plant.
  • EP 0 672 618 A1 relates to a process for recovering elemental sulfur from a gas mixture containing hydrogen sulfide. According to the described method, it is possible to convert sulfur-containing carbon compounds into hydrogen sulfide by hydrolysis. In a thermal section of a Claus plant, hydrogen sulphide is reacted with atmospheric oxygen to form sulfur dioxide, whereupon in the catalytic part a synproportionation of hydrogen sulphide with the generated sulfur dioxide to elemental sulfur and water takes place. To prevent environmental pollution by leaking or released hydrogen sulfide, the leaving the Claus plant gas is subjected to afterburning. In this way, the hydrogen sulfide not consumed in the synproportionation is converted to sulfur dioxide, whose toxicity is much less critical than that of hydrogen sulfide.
  • the sulfur component fraction and the carbon dioxide fraction contained in the sour gas should be recovered separately in as pure a form as possible.
  • the known absorption processes can not separately separate sulfur components on the one hand and carbon dioxide on the other hand in a high selectivity from a gas mixture.
  • the common separation of carbon dioxide and sulfur components in a common sour gas fraction which is supplied for further processing of a Claus plant and is then inexpensively converted in the process of the invention into elemental sulfur and carbon dioxide.
  • chemically and physically acting washing processes can be used for the joint separation of carbon dioxide and sulfur components.
  • an acid gas which consists essentially of carbon dioxide and sulfur components, in particular H 2 S, COS and Mehrkaptanen
  • the elemental sulfur and the water, which are formed in the Claus process by the reaction of the sulfur components with the oxygen, are condensed out of the residual gas, so that a strong accumulation of carbon dioxide takes place.
  • the residual gas leaving the Claus plant can be subjected to a downstream gas purification process.
  • a hydrogenation can be provided in which the sulfur components which are present in the residual gas in addition to H 2 S are hydrogenated to H 2 S.
  • the residual gas is subsequently quenched and subjected to selective scrubbing, preferably with a chemical absorbent, whereby the H 2 S still present in the residual gas is largely removed.
  • the residual gas consists essentially of carbon dioxide, water and small amounts of carbon monoxide and hydrogen.
  • the SCOT ® method S bright C laus O ff gas T reatment
  • a removal of said components by pressure and / or temperature changes of the residual gas can be achieved.
  • it may be provided to free the residual gas after carrying out a residual gas purification process by means of a gas cooler or a quench column of most of the water vapor and then to compress the liquefaction of the carbon dioxide.
  • Carbon monoxide and hydrogen can then be removed from the liquefied carbon dioxide in a suitable separator.
  • the sour gas supplied to the Claus plant contains inert gas components in addition to carbon dioxide and sulfur components, at least the expense of subsequent separation can be kept low, since no additional inert gas components are supplied to the desulfurization process according to the invention.
  • inventively provided use of technically pure oxygen allows in a particularly advantageous manner for a given amount of sour gas and a smaller dimensioning of the Claus plant and an optionally provided device for residual gas purification, so that the additional costs necessary for the provision of technically pure oxygen can be compensated ,
  • a device suitable for carrying out the method comprises, in addition to the usual components, in particular a connecting line, which has an inlet of the combustion chamber of the Claus plant with one of the Claus plant downstream gas supply or a downstream of the Claus plant reservoir for the residual gas connects. Furthermore, a control device is provided on the connecting line in order to control the admixing of the process-specific residual gas as needed at the inlet.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Environmental & Geological Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Analytical Chemistry (AREA)
  • Biomedical Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Treating Waste Gases (AREA)
  • Gas Separation By Absorption (AREA)
  • Carbon And Carbon Compounds (AREA)

Description

Die Erfindung betrifft ein Verfahren zur Entschwefelung, wobei ein Gasgemisch zur Separation saurer Gaskomponenten einem Abtrennprozess unterzogen wird, bei dem ein Kohlendioxid und Schwefelverbindungen, insbesondere Schwefelwasserstoff, enthaltendes Sauergas gebildet wird. Bei dem Verfahren werden saure Gaskomponenten zunächst mit einem geeigneten Absorptionsmittel aus dem Gasstrom entfernt und damit von einer Nutzgaskomponente getrennt. Bei der Regeneration des in einem Kreislauf geführten Absorptionsmittels werden die enthaltenen Sauergaskomponenten freigesetzt und nachfolgend einer Claus-Anlage zugeführt.The invention relates to a process for desulfurization, wherein a gas mixture for separating acidic gas components is subjected to a separation process in which a sour gas comprising carbon dioxide and sulfur compounds, in particular hydrogen sulfide, is formed. In the process, acidic gas components are first removed from the gas stream with a suitable absorbent and thus separated from a Nutzgaskomponente. During the regeneration of the recirculated absorbent the sour gas components contained are released and subsequently fed to a Claus plant.

Üblicherweise wird das Claus-Verfahren derart durchgeführt, dass das Sauergas mit Luft verbrannt wird, wobei der Schwefelwasserstoff (H2S) mit dem in der Verbrennungsluft enthaltenen Sauerstoff (O2) zu elementarem Schwefel und Wasser (H2O) umgesetzt wird und wobei der elementare Schwefel (S) durch nachfolgende Kühlung in Kondensatoren abgeschieden wird (" Ullmanns Enzyklopädie der technischen Chemie, Band 10, 4. Auflage 1975, Seite 594 ). Mit den bekannten Claus-Verfahren kann üblicherweise eine Ausbeute von bis zu 98 % erreicht werden. Um eine zusätzliche Reinigung des Restgases zu erreichen, kann dieses einem Restgasreinigungsverfahren unterzogen werden. Während der in dem Claus-Verfahren gebildete elementare Schwefel entnommen und kommerziell verwertet werden kann, wird das gereinigte Restgas üblicherweise ungenutzt an die Umgebung abgegeben.Usually, the Claus process is carried out such that the sour gas is burned with air, wherein the hydrogen sulfide (H 2 S) with the oxygen contained in the combustion air (O 2 ) to elemental sulfur and water (H 2 O) is reacted and the elemental sulfur (S) is separated by subsequent cooling in capacitors (" Ullmann's Encyclopedia of Industrial Chemistry, Volume 10, 4th edition 1975, page 594 ). With the known Claus process usually a yield of up to 98% can be achieved. In order to achieve additional purification of the residual gas, this can be subjected to a residual gas purification process. While the elemental sulfur formed in the Claus process can be withdrawn and utilized commercially, the purified residual gas is usually released into the environment unused.

Da Kohlendioxid als sogenanntes Klimagas zu dem globalen Treibhauseffekt beiträgt, besteht das Bedürfnis, die zusätzliche Freisetzung von Kohlendioxid zu vermeiden. Des Weiteren sind gegenwärtig auch Verfahren bekannt, die große Mengen an Kohlendioxid als Prozessgas benötigen. So kann Kohlendioxid beispielsweise bei der Ölförderung zu einer Erhöhung der Ausbeute eingesetzt werden, wobei Kohlendioxid in ein Ölreservoir injiziert wird ("Enhanced Oil Recovery" EOR). Sowohl für die Sequestrierung von Kohlendioxid zur Emissionsvermeidung als auch für die technische Nutzung muss das Kohlendioxid üblicherweise mit einem erheblichen Aufwand von weiteren Komponenten, beispielsweise Stickstoff getrennt werden.Since carbon dioxide contributes to the global greenhouse effect as so-called climate gas, there is a need to increase the additional release of carbon dioxide avoid. Furthermore, processes are also currently known which require large amounts of carbon dioxide as a process gas. Carbon dioxide, for example, can be used to increase the yield during oil production, whereby carbon dioxide is injected into an oil reservoir ("Enhanced Oil Recovery" EOR). Both for the sequestration of carbon dioxide to avoid emissions as well as for technical use, the carbon dioxide usually has to be separated with a considerable effort of other components, such as nitrogen.

Die Druckschrift EP 0 059 412 A2 betrifft ein Verfahren zur Regelung der Ballastgasmenge bei einem Verbrennungsprozess, insbesondere bei dem Betrieb einer Claus-Anlage, wobei das gebildete Restgas in üblicher Weise an die Umgebung abgegeben wird. Um eine optimale Verbrennung zu erreichen, ist vorgesehen, Luft und technisch reinen Sauerstoff zuzuführen, wobei das Verhältnis von Luft und technisch reinem Sauerstoff an den jeweils vorliegenden Inertgasanteil in dem Brenngas angepasst wird. Der Begriff technisch reiner Sauerstoff bezieht sich auf ein Gas, welches zum größten Teil aus Sauerstoff besteht und in einem üblichen großtechnischen Gewinnungsverfahren gebildet ist. Die Reinheit beträgt üblicherweise mehr als 90 %, bei kryogenen Zerlegungsverfahren typischerweise zumindest 98 %.The publication EP 0 059 412 A2 relates to a method for controlling the amount of ballast gas in a combustion process, in particular in the operation of a Claus plant, wherein the residual gas formed is discharged in a conventional manner to the environment. In order to achieve optimum combustion, it is provided to supply air and technically pure oxygen, wherein the ratio of air and technically pure oxygen is adapted to the respectively present inert gas in the fuel gas. The term technically pure oxygen refers to a gas which for the most part consists of oxygen and is formed in a conventional large-scale production process. The purity is usually more than 90%, in the case of cryogenic decomposition methods typically at least 98%.

Aus dem Aufsatz von H. Fischer in Chemie-Ing.-Techn. 39 (1967), Seite 515 bis 520 ist des Weiteren bekannt, bei einem Anteil des Schwefelwasserstoffes zwischen 20 bis etwa 5 Vol.-% einer Claus-Anlage technisch reinen Sauerstoff für die Umsetzung des Sauergases zuzuführen, um eine ausreichend hohe Verbrennungstemperatur zu erreichen. Das Restgas wird auch dabei in üblicher Weise als Abgas freigesetzt.From the essay by H. Fischer in Chemical Engineering Techn. 39 (1967), pages 515-520 Furthermore, it is known, in a proportion of hydrogen sulfide between 20 to about 5 vol .-% of a Claus plant to supply technically pure oxygen for the implementation of the acid gas in order to achieve a sufficiently high combustion temperature. The residual gas is also released in the usual way as exhaust gas.

In EP 1914 294 A1 ist ein gattungsgemäßes Verfahren zur Entfernung von Schwefelkomponenten, beispielsweise Schwefelwasserstoff und Mercaptanen, aus Erdgas beschrieben. Zur Entfernung von Schwefelwasserstoff und Kohlendioxid erfolgt zunächst eine Wäsche des Erdgases, woraufhin eine Umwandlung der Mercaptane in Schwefelwasserstoff in einem möglichst großen Gasvolumen erfolgt. Kohlendioxid und Schwefelwasserstoff werden anschließend einer Claus-Anlage zugeführt, in der dann Schwefel gewonnen wird. Das aus dem Claus-Reaktor austretende Restgas kann in einem SCOT®-Prozess weiterbehandelt werden, um den Schwefelgehalt des Restgases weiter zu senken.In EP 1914 294 A1 is a generic method for removing sulfur components, such as hydrogen sulfide and mercaptans, described from natural gas. For the removal of hydrogen sulfide and carbon dioxide is first carried out a scrubbing of the natural gas, whereupon a conversion of the mercaptans into hydrogen sulfide takes place in the largest possible volume of gas. Carbon dioxide and hydrogen sulfide are then fed to a Claus plant in which sulfur is then recovered. Emerging from the Claus reactor residual gas can be further treated in a SCOT ® process to reduce the sulfur content of the residual gas on.

In WO 2008/103467 A1 ist ein Verfahren beschrieben, mit dem Wasserstoff und Kohlendioxid aus einem Synthesegasstrom gewonnen werden können. Bei diesem Verfahren wird in einem ersten Schritt Schwefelwasserstoff und in einem zweiten Schritt Kohlendioxid aus dem Gasgemisch entfernt. Hierzu werden unterschiedliche Absorber eingesetzt. Grundsätzlich ist es dabei möglich, dass der entnommene Schwefelwasserstoff zur Schwefelgewinnung eingesetzt wird.In WO 2008/103467 A1 describes a method by which hydrogen and carbon dioxide can be recovered from a syngas stream. In this method, hydrogen sulfide is removed in a first step and carbon dioxide in a second step from the gas mixture. For this purpose, different absorbers are used. In principle, it is possible that the withdrawn hydrogen sulfide is used for sulfur recovery.

Aus US 5,628,977 ist ein Verfahren zur Entschwefelung von schwefelwasserstoffhaltigen Abgasen bekannt. Ein Großteil des Schwefelwasserstoffs wird in einer Claus-Anlage aus den Abgasen entfernt. Das die Claus-Anlage verlassende Gas enthält beispielsweise wegen unvollständiger Verbrennung Schwefelwasserstoff, Blausäure, Ammoniak, Carbonylverbindungen, Phenole und andere Kohlenwasserstoffe. Um die Umweltbelastung zu verringern, wird vorgeschlagen, den Brennwert der in dem Restgas vorhandenen Gasen, insbesondere Kohlenmonoxid, Wasserstoff, Schwefelwasserstoff, Schwefeldämpfen und organischen Verbindungen, durch eine Verbrennung zu nutzen. Das bei dem Verbrennungsprozess entstehende Schwefeldioxid wird rezykliert und der Claus-Anlage zugeführt.Out US 5,628,977 is a method for the desulfurization of hydrogen sulfide-containing exhaust gases known. Most of the hydrogen sulfide is removed from the exhaust gases in a Claus plant. The leaving the Claus plant gas contains, for example, due to incomplete combustion hydrogen sulfide, hydrogen cyanide, ammonia, carbonyl compounds, phenols and other hydrocarbons. In order to reduce the environmental impact, it is proposed to use the calorific value of the gases present in the residual gas, in particular carbon monoxide, hydrogen, hydrogen sulfide, sulfur vapor and organic compounds, by combustion. The sulfur dioxide produced in the combustion process is recycled and fed to the Claus plant.

EP 0 672 618 A1 betrifft ein Verfahren zur Gewinnung von elementarem Schwefel aus einem Schwefelwasserstoff enthaltenden Gasgemisch. Gemäß dem beschriebenen Verfahren ist es möglich, schwefelhaltige Kohlenstoffverbindungen mittels Hydrolyse in Schwefelwasserstoff umzuwandeln. In einem thermischen Teil einer Claus-Anlage wird Schwefelwasserstoff mit Luftsauerstoff zu Schwefeldioxid umgesetzt, woraufhin in dem katalytischen Teil eine Synproportionierung von Schwefelwasserstoff mit dem erzeugten Schwefeldioxid zu elementarem Schwefel und Wasser erfolgt. Um Umweltbelastungen durch austretenden bzw. freigesetzten Schwefelwasserstoff zu verhindern, wird das die Claus-Anlage verlassende Gas einer Nachverbrennung unterzogen. Auf diese Weise wird der bei der Synproportionierung nichtverbrauchte Schwefelwasserstoff zu Schwefeldioxid umgesetzt, dessen Toxizität wesentlich unkritischer als die von Schwefelwasserstoff ist. EP 0 672 618 A1 relates to a process for recovering elemental sulfur from a gas mixture containing hydrogen sulfide. According to the described method, it is possible to convert sulfur-containing carbon compounds into hydrogen sulfide by hydrolysis. In a thermal section of a Claus plant, hydrogen sulphide is reacted with atmospheric oxygen to form sulfur dioxide, whereupon in the catalytic part a synproportionation of hydrogen sulphide with the generated sulfur dioxide to elemental sulfur and water takes place. To prevent environmental pollution by leaking or released hydrogen sulfide, the leaving the Claus plant gas is subjected to afterburning. In this way, the hydrogen sulfide not consumed in the synproportionation is converted to sulfur dioxide, whose toxicity is much less critical than that of hydrogen sulfide.

Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren mit den eingangs beschriebenen Merkmalen anzugeben, welches bei einem geringen Aufwand eine Nutzung des in dem Sauergas enthalten Kohlendioxids ermöglicht.The invention has for its object to provide a method with the features described above, which allows for a low cost, a use of the carbon dioxide contained in the sour gas.

Die Aufgabe wird erfindungsgemäß durch ein Verfahren gemäß Patentanspruch 1 gelöst. Gemäß der vorliegenden Erfindung sollen die in dem Sauergas enthaltene Schwefelkomponentenfraktion und die Kohlendioxidfraktion in möglichst reiner Form getrennt gewonnen werden. Mit den aus dem Stand der Technik bekannten Verfahren ist eine solche weitgehend reine Trennung nur unter sehr hohem Aufwand möglich, da die bekannten Absorptionsprozesse Schwefelkomponenten einerseits und Kohlendioxid andererseits nicht in einer hohen Selektivität aus einem Gasgemisch getrennt abtrennen können. Vergleichsweise einfach ist dagegen die gemeinsame Abtrennung von Kohlendioxid und Schwefelkomponenten in einer gemeinsamen Sauergasfraktion, die zur weiteren Verarbeitung einer Claus-Anlage zugeführt wird und die dann im Rahmen des erfindungsgemäßen Verfahrens kostengünstig in elementaren Schwefel und Kohlendioxid umgewandelt wird. Zur gemeinsamen Abtrennung von Kohlendioxid und Schwefelkomponenten können zum Beispiel chemisch und physikalisch wirkende Waschverfahren angewandt werden. Erfindungsgemäß wird der Claus-Anlage ausschließlich technisch reiner Sauerstoff als Sauerstoff enthaltendes Reaktionsgas zugeführt. Dadurch wird in besonders vorteilhafter Weise erreicht, dass bei der Aufbereitung des Sauergases keine Inertgasanteile zugeführt werden, die nachträglich mit einem großen Aufwand von dem Kohlendioxid getrennt werden müssen.The object is achieved by a method according to claim 1. According to the present invention, the sulfur component fraction and the carbon dioxide fraction contained in the sour gas should be recovered separately in as pure a form as possible. With the methods known from the prior art, such a largely pure separation is possible only at very high cost, since the known absorption processes can not separately separate sulfur components on the one hand and carbon dioxide on the other hand in a high selectivity from a gas mixture. comparatively simply, however, the common separation of carbon dioxide and sulfur components in a common sour gas fraction, which is supplied for further processing of a Claus plant and is then inexpensively converted in the process of the invention into elemental sulfur and carbon dioxide. For the joint separation of carbon dioxide and sulfur components, for example, chemically and physically acting washing processes can be used. According to the Claus system is fed exclusively technically pure oxygen as the reaction gas containing oxygen. As a result, it is achieved in a particularly advantageous manner that in the preparation of the acid gas no inert gas components are supplied, which must be subsequently separated with a great deal of the carbon dioxide.

Um Anteile von Wasserstoff und/oder Kohlenmonoxid zu Wasser bzw. Kohlendioxid umzusetzen ist erfindungsgemäß eine Nachverbrennung des Restgases mit technisch reinem Sauerstoff, die vorzugsweise katalytisch erfolgt, vorgesehen. Sofern das ursprünglich der Claus-Anlage zugeführte Sauergas im Wesentlichen aus Schwefelverbindungen und Kohlendioxid besteht, enthält das Restgas nach der Durchführung eines Restgasreinigungsverfahrens und einer Nachverbrennung zur Entfernung von Wasserstoff und/oder Kohlenmonoxid nur noch nahezu reines Kohlendioxid und Wasserdampf, der bei der weiteren Behandlung des Restgases auskondensiert wird. Des Weiteren können auch bekannte Verfahren zur Gastrocknung angewandt werden um den Wassergehalt weiter zu reduzieren. Das nach der Entfernung von Wasser im Wesentlichen aus Kohlendioxid bestehende Restgas wird zur Sequestrierung, d.h. insbesondere zur Einlagerung in geologischen Formationen wie Erdöllagerstätten, Erdgaslagerstätten, Äquiferen, Kohleflözen oder in der Tiefsee, oder zur technischen Nutzung üblicherweise komprimiert oder verflüssigt, wobei insbesondere auch eine Zwischenlagerung oder ein Transport des Kohlendioxids vorgesehen sein können. Abhängig von der vorgesehenen weiteren Verwendung des Kohlendioxids beträgt die Reinheit im gasförmigen Zustand zumindest 80 Vol.-%, bevorzugt 90 Vol.-%, besonders bevorzugt 95 Vol.-%.In order to convert proportions of hydrogen and / or carbon monoxide to water or carbon dioxide, an afterburning of the residual gas with technically pure oxygen, which preferably takes place catalytically, is provided according to the invention. If the sour gas originally supplied to the Claus plant consists essentially of sulfur compounds and carbon dioxide, the residual gas after carrying out a residual gas purification process and an afterburning to remove hydrogen and / or carbon monoxide contains only almost pure carbon dioxide and water vapor, which in the further treatment of Remaining gas is condensed out. Furthermore, known methods for gas drying can be used to further reduce the water content. The residual gas consisting essentially of carbon dioxide after the removal of water is usually compressed or liquefied for sequestration, in particular for storage in geological formations such as crude oil deposits, natural gas deposits, equifers, coal seams or in the deep sea, or for technical use, in particular also an intermediate storage or a transport of carbon dioxide can be provided. Depending on the intended further use of the carbon dioxide, the purity in the gaseous state is at least 80% by volume, preferably 90% by volume, particularly preferably 95% by volume.

Im Rahmen einer bevorzugten Ausgestaltung des erfindungsgemäßen Verfahrens ist vorgesehen, dass bei Überschreiten einer maximal zulässigen Brenntemperatur innerhalb der Brennkammer der Claus-Anlage abströmseitig ein Anteil des prozesseigenen Restgases entnommen und zur Kühlung gemeinsam mit dem technisch reinen Sauerstoff der Brennkammer zugeführt wird. Durch die beschriebenen Maßnahmen ist eine präzise Steuerung des Brennvorganges möglich, ohne dass die Aufkonzentration von Kohlendioxid beeinträchtigt wird.Within the scope of a preferred embodiment of the method according to the invention, it is provided that, when a maximum permissible firing temperature within the combustion chamber of the Claus plant is exceeded, a fraction of the process-specific residual gas is withdrawn and supplied to the combustion chamber together with the technically pure oxygen for cooling. By the measures described a precise control of the burning process is possible without the concentration of carbon dioxide is affected.

Bei einem Sauergas, welches im Wesentlichen aus Kohlendioxid und Schwefelkomponenten, insbesondere H2S, COS und Mehrkaptanen, besteht kann so eine weitgehend vollständige Separation erreicht werden. Der elementare Schwefel und das Wasser, die in dem Claus-Prozess durch die Reaktion der Schwefelkomponenten mit dem Sauerstoff gebildet werden, werden aus dem Restgas herauskondensiert, so dass eine starke Anreicherung des Kohlendioxids erfolgt. Um noch verbleibende Reste von Schwefelverbindungen zumindest weitgehend zu entfernen, kann das die Claus-Anlage verlassende Restgas einem nachgeordneten Gasreinigungsverfahren unterzogen werden. So kann beispielsweise eine Hydrierung vorgesehen sein, bei der die neben H2S in dem Restgas enthaltenden Schwefelkomponenten zu H2S hydriert werden. Das Restgas wird nachfolgend gequencht und einer selektiven Wäsche, vorzugsweise mit einem chemischen Absorptionsmittel, unterzogen, wobei das noch in dem Restgas vorhandene H2S weitgehend entfernt wird. Nach der zusätzlichen Entfernung von Schwefelkomponenten besteht das Restgas im Wesentlichen aus Kohlendioxid, Wasser und geringen Anteilen von Kohlenmonoxid und Wasserstoff. Als Restgasreinigungsverfahren ist beispielsweise das SCOT®-Verfahren (Shell Claus Off gas Treatment) geeignet.In an acid gas, which consists essentially of carbon dioxide and sulfur components, in particular H 2 S, COS and Mehrkaptanen, so a largely complete separation can be achieved. The elemental sulfur and the water, which are formed in the Claus process by the reaction of the sulfur components with the oxygen, are condensed out of the residual gas, so that a strong accumulation of carbon dioxide takes place. In order to remove remaining residues of sulfur compounds at least substantially, the residual gas leaving the Claus plant can be subjected to a downstream gas purification process. Thus, for example, a hydrogenation can be provided in which the sulfur components which are present in the residual gas in addition to H 2 S are hydrogenated to H 2 S. The residual gas is subsequently quenched and subjected to selective scrubbing, preferably with a chemical absorbent, whereby the H 2 S still present in the residual gas is largely removed. After the additional removal of sulfur components, the residual gas consists essentially of carbon dioxide, water and small amounts of carbon monoxide and hydrogen. As a residual gas purification method, for example, the SCOT ® method ( S bright C laus O ff gas T reatment) is suitable.

Zusätzlich zu einer Nachverbrennung von Wasserstoff und/oder Kohlenmonoxid mit technisch reinem Sauerstoff kann auch eine Entfernung der genannten Komponenten durch Druck- und/oder Temperaturänderungen des Restgases erreicht werden. So kann beispielsweise vorgesehen sein, das Restgas nach der Durchführung eines Restgasreinigungsverfahrens mittels eines Gaskühlers oder einer Quenchkolonne vom größten Teil des Wasserdampfes zu befreien und danach zur Verflüssigung des Kohlendioxides zu komprimieren. Kohlenmonoxid und Wasserstoff können dann in einer geeigneten Trenneinrichtung aus dem verflüssigten Kohlendioxid entfernt werden.In addition to an afterburning of hydrogen and / or carbon monoxide with technically pure oxygen, a removal of said components by pressure and / or temperature changes of the residual gas can be achieved. Thus, for example, it may be provided to free the residual gas after carrying out a residual gas purification process by means of a gas cooler or a quench column of most of the water vapor and then to compress the liquefaction of the carbon dioxide. Carbon monoxide and hydrogen can then be removed from the liquefied carbon dioxide in a suitable separator.

Sofern das der Claus-Anlage zugeführte Sauergas neben Kohlendioxid und Schwefelkomponenten noch Inertgasanteile enthält, kann zumindest der Aufwand einer nachträglichen Trennung gering gehalten werden, da bei dem erfindungsgemäßen Verfahren zur Entschwefelung keine zusätzlichen Inertgaskomponenten zugeführt werden.If the sour gas supplied to the Claus plant contains inert gas components in addition to carbon dioxide and sulfur components, at least the expense of subsequent separation can be kept low, since no additional inert gas components are supplied to the desulfurization process according to the invention.

Die erfindungsgemäß vorgesehene Verwendung von technisch reinem Sauerstoff ermöglicht auf besonders vorteilhafte Weise bei einer vorgegebenen Menge an Sauergas auch eine kleinere Dimensionierung der Claus-Anlage und einer optional vorgesehen Vorrichtung zur Restgasreinigung, so dass die für die Bereitstellung des technisch reinen Sauerstoffs erforderlichen Zusatzkosten ausgeglichen werden können.The inventively provided use of technically pure oxygen allows in a particularly advantageous manner for a given amount of sour gas and a smaller dimensioning of the Claus plant and an optionally provided device for residual gas purification, so that the additional costs necessary for the provision of technically pure oxygen can be compensated ,

Eine für die Durchführung des Verfahrens geeignete Vorrichtung umfasst neben den üblichen Komponenten insbesondere eine Verbindungsleitung, die einen Einlass der Brennkammer der Claus-Anlage mit einer der Claus-Anlage nachgeordneten Gasführung oder einem der Claus-Anlage nachgeordneten Vorratsbehälter für das Restgas verbindet. Des Weiteren ist an der Verbindungsleitung eine Steuereinrichtung vorgesehen, um an dem Einlass die Beimischung des prozesseigenen Restgases bedarfsgerecht zu steuern.A device suitable for carrying out the method comprises, in addition to the usual components, in particular a connecting line, which has an inlet of the combustion chamber of the Claus plant with one of the Claus plant downstream gas supply or a downstream of the Claus plant reservoir for the residual gas connects. Furthermore, a control device is provided on the connecting line in order to control the admixing of the process-specific residual gas as needed at the inlet.

Claims (7)

  1. A method for desulphurisation,
    wherein a gas mixture is subjected to a separating process for the separation of acid gas components, during which an acid gas is formed, which contains a carbon dioxide and sulphurous compounds, in particular hydrogen sulphide,
    wherein the acid gas is fed to a Claus plant for separating the elementary sulphur, with exclusively technically pure oxygen being supplied to the Claus plant as an oxygen-containing reaction gas, and wherein carbon dioxide with a purity of at least 80 % by volume is withdrawn downstream of the Claus plant, permitting an immediate sequestration or technical use,
    characterised in that the residual gas leaving the Claus plant is subjected to post-combustion with technically pure oxygen in order to remove hydrogen and carbon monoxide and in that water vapour is condensed out of the residual gas.
  2. The method according to claim 1, characterised in that catalytic post-combustion of the residual gas is carried out.
  3. The method according to claim 1 or 2, characterised in that in case a maximum admissible combustion temperature is exceeded in a combustion chamber of the Claus plant, an admixture is added which is a proportion of the process-related residual gas withdrawn from the outflow side relative to the Claus plant.
  4. The method according to one of claims 1 to 3, characterised in that during the separating process all acid gas components are separated together out of the gas mixture and recovered in a joint fraction as an acid gas.
  5. The method according to one of claims 1 to 4, characterised in that the separating process encompasses washing the gas mixture using a physical and/or chemical absorption agent and the regeneration of the absorption agent.
  6. The method according to one of claims 1 to 5, characterised in that the residual gas leaving the Claus plant is subjected to a residual gas cleaning process, in particular a Scot® process, in order to at least substantially remove any residues of sulphur compounds.
  7. The method according to one of claims 1 to 6, characterised in that the residual gas is compressed for further usage.
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WO2010040495A2 (en) 2010-04-15
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PL2365938T3 (en) 2018-01-31
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CN102177089A (en) 2011-09-07
JP2012504538A (en) 2012-02-23

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